Colorimeter



Oct 8, 1940. w. F. LANGELIER COLORIIETER Filed NOV. 1, 1957 4 Sheets-Sheet l IATVENTOR. W/LFRED E LANGfL IER BY Y W/MMW FIG. I

ms ATTORNEY.

. 1940- w. F. LANGELIER COLORIIE'I'EH 4 Sheets-Sheet 2 Filed Nov. 1. 1937 FIG. 6'

INVENTOR. W/LFREO E LANGELIER ms ATTORNEY.

' Oct. 8, 1940. w. F. LANGELIER cononmm'za Filed Nov. 1. 1937 4 Sheets-Sheet 3 FIG. I2

Fig. I0

INVENTOQR.

LANGfL/ER BY z/m W/LFRED E HIS ATTORNEY.

w. F. LANGELIER cownmmnn Filed Nov. ,1, 1957 4 Sheets-Skeet, 4

INVENTOR. W/LFRED r: LANGtZ/ER HIS ATTORNEY.

Patented Oct. 8, 1940 UNITED STATES PATENT OFFICE Wilfred E Calif. Application Hovembcr 1, 1987, Serlal No. 172,251 1'! Claims. (Cl- 88-14) This invention relates to colorimeters, and is sponding to extreme alkalinity. These standard primarily concerned with a colorimeter inwhich solutions are juxtaposed so as to cause a ray of the color of an unknown is determined by comlight to pass therethrough, the total depth of the parison with two solutions of known colors. two solutions interposed in the path or the light 5 Such an instrument is known as a bicolorimeter. being constant and equal to the depth of the un- I In a bicolorimeter the color of the unknown known solution, and the relative depths of these solution is measured by viewing it by light passtwo solutions being adjustable, whereby the color 'ing through a predetermined depth of the soluof the unknown solution can be matched by 9. tion, and comparing the color with that oi the combination of the depths of the standard solul0 two solutions of known colors, which are contions. The present invention is particularly contained in suitable vessels so arranged that they cerned with the last described method of measmay be observed by transmitted light of the same uring the assumed shade of the solution or the intensity as that passing through the unknown, indicator in the unknown.

' the total depth of the known solutions being The theoretical basis .for the two-solution sysequal to that of the unknown solution, and the tem of colorimetry contemplated according to the II relative depths of the known solutions being varipresent invention is known. It is that indicators able and measurable. Such a colorimeter may behave like weak acids or weak bases, the dissobe employed whenever the color of the unknown ciated and undissociated forms of which have is produced by coloring bodies which may assume diflerent colors and forms, and that the color 9,0 two forms or shades, and the total concentration which is observed by transmitted light depends to of such bodies in the unknown is determinable. upon the relative concentrations of the dissoci- The colorimeter according to the present inated and undissociated forms of the ihdicator. vention is particularly useful in, and is especially The condition of equilibrium in the solution is designed for, the determination of the pH or hydetermined by the pH of the unknown, and the g5 'rogen ion exponent of water or other liquids, but color assumed by the solution resulting from the may be employed or adapted for other uses. It addition of a small quantity of the indicator to is suitable for the determination of the pH withthe unknown is, therefore, a measure of its pH.

out the use of buffer solutions, although it is un- In general, such a solution of the unknown conderstood that the use of buffer solutions therein taining an indicator which assumes a transition is not excluded. shade at the pH oi! the unknown, will contain a 80 In the determination of the pH of an unknown certain concentration of the indicatorin the acid solution, such as water, a measured quantity of form and a certain concentration of the indian indicator which assumes a transition shade at cator in the alkaline form, the sum of these conthe pH of the unknown is added thereto. When centrations being equal to the concentration of the expected pH of the solution is not known. the indicator added. The relationship between as several indicators are successively added until these two concentrations establishes the equlibrione is found which assumes such a shade, and the um conditions and the pH of the unknown. This letter is e p y using fIeSh p e f t relationship is, according to the present invention, unknown. The h d s um d by the Indicate! readily determined by measuring the relative 4 is then compared with a standard, which m be depths f juxtaposed standard solutions, as dein the form of a translucent material carrying scribed above, which will yield a by trans pigment it being W necessary to provide mitted light equal to that of the color by transsefles of Such matenals of varying Shades; or mitted light of the indicator solution in the unseries of buffered solutions of fixed pH containknown ing the same indicator in the same concentration may be employed. According to still another g e equilibrium method, the shade is compared with a combinal of t e m and e R of the non of two solutions, each containing the indi known has been described in the scientific literature, and it is unnecessary to present a detailed cator in the same concentration as the unknown, one having the indicator fully transformed into discussion thereof m this Specification, beyond 50 the acid form, and the other having the indicator presenting the equations 1 which the 6911ifully transformed into thebasic or alkaline form, hmtion 0f the instrument p Quantitathereby providing a standard solution having a tively. n the ease of an indicator the 11116 5 01- known color corresponding to extreme acidity, and .ated form of which has acid properties, the equia second standard solution having a color corre-' librium is governed by the following equation, de- 5 rivable from the action: I

equation for the law of mass wherein [I+l.represents the concentration of the acid form of the indicator (which has the acid color), [OH-l represents the concentration of the hydroxyl ions [IOH] represents the concentration of the undissociated form of the indicator (which has the alkaline color). and K101! is the ionization constant. In the case of an indicator of this type the indicator constant is defined by the equation:

-K1 wherein Kw is the ionization product of water, and K1 is the indicator constant.

In either type of indicator, the color assumed in a solution is fixed by the ratio oi the concentrations of the alkaline and acid forms. Moreover, for either type,-this ratio is equal to the ratio: I

so that. the hydrogen ion concentration may be expressed by the equation:

pfl+log-"- zg g fi i +plir wherein pH is the hydrogen exponent or hydrogen ion exponent, and is equal to ,log [11+]: [alkaline form] represents the concentration of the alkaline form of the indicator, 1. e., [1-] in the case of the first type of indicator described above, and [10H] in the case of the second type of indicator; [acid form] represents the concentration of the acid form of the indicator, 1. e., [HI] in the case of the first type of indicator, and [1+] in the case of the second type of indicator; and pKr is a constant dependent upon the indicator constant, defined by the relationship:

all logarithms being common logarithms. It should be noted that the value pm varies with the temperature, and also with the electrolyte content of the solution.

It is an object of the present invention to provide a device for conveniently determining the hydrogen ion concentration or pH of an 'unknown solution, by providing means for bringing two solutions consisting entirely or predominantly of the indicator in its acid and alkaline forms, respectively, into juxtaposition in any desired ratio of depths and means for expressing this ratio of depths in a form which will permit a simple determination of the pH. It is-a further object to provide a colorimeter for comparing the color of an unknown with a pair of solutions. I plates a mechanical arrangement for varying the rect reading oi the pH;

tions of known colors in which the colorof the I juxtaposed solutions may be easily compared with the color of piece..and in which-the optical system is simplified. A 'iurtherlobject is to arrange the vessels containing the solutions inthe colorimeter so as to facilitate the removal of the vessels therefrom for solutions, and to permit their replacement with a minimum of adjustment. Another object is to provide means formaking a simple compensation for the turbidity or natural color of the unknown; A still further object is to provide a dial which will permit the direct reading of the pH without the necessityof calcula- The presentinvention further contemrelative depths of two solutions'oi' standard colors by means of an actuating-indicating means the position of which is a linear function of the pH. Other objects of the invention will appear from the following specification. taken in cone nection with the drawings'forming a part thereof, which illustrate representative embodiments thereof, in which:

. Figure l is a rear orimeter;

Figure 2 is-a sectional plan view, taken along line 2-2 of Figure l; t I

Figure 3 .is a side elevational view of thevcolorimeter;

Figure 4 is a perspective view of the clamp for supporting the movable cup;

Figure 5 is a rear perspective view of the cabinet of the colorimeter, with the cups, top and one side wall removed therefrom;

Figure 8 is a perspective view of the clamp for supporting one of the fixed telescoping cups;

Figure 7 is a fragmental elevation view of the front of the colorimeter showing the dial;

Figure 8 is a view similar to Figure 7, showing a modified form 01' the dial, adapted for the dielevation' view of the col- Figure9 isa sectional of Figure 8; a

Figure 10 is a rear elevational view of fied form of the colorimeter;

Figure 11 is a sectional plan view of them]- orimeter shown in Figure 10, taken along line ll-Il of Figure 12;

Figure 12 is a fragments-l vertical sectional view taken along line I'I-l! of Figure-11;

Figure 13 is an elevation view of the cam;

v Figure 14'is a perspective view of a portion of a cup and of the supporting bar;

Figure 15 is a fragmental side elevational view of the colorimeter showing the reading-discs;

Figure 16 is a sectional view taken on line IOI0 of Figure 11.

Referring to the drawings. and particularly to Figures 1 to 7, the colorimeter comprises a cabinet I, provided with a hinged door 2, and with a ceiling I; a front wall structed to exclude light from the interior save through apertures in the fioor. The cabinet is supported by a base 8, carrying a reflector i, hingedly supported by a pair of legs I.

r A- cup 9, having a fiat translucent bottom, such as a glass test tube with a fiat fioor, and-adapted a modi- .to contain the unknown solution, is removably mounted within the cabinet by means of a resilient clamp l0, secured to a wall of the cabinet, the cup normally resting on the floor 5 and abutting 'a positioning plate II which has an outline to fit the cup 9. A second cup II, also having a flat, translucent botto is mounted .theunknown'inasingleeye' view taken on line 9-4 I, and fioor I, contelescopically within and eccentrically with respect to the cup 6 at a predetermined distance above the bottom thereof, by-means of a clampl3. This clamp is provided with a flat facet l4 facing the center of the cabinet, whereby the eccentric mounting of the cup 12 is facilitated. The clamp I3 is pivotally supported on a chat 16 by means of a rearwardly extending mg" and a horizontal pin 11, the cleat 15 being attachedto the front wall 4 of the cabinet.

A spacing bar I6 is secured to the side wall of the cabinet by a hinge l3 having a vertical axis of rotation. The upper surface of the spac ing bar is spaced from the top of the floorl by a distance equal to the depth through which it is desired to observe the unknown solution. This distance is hereinafter designated as the observing depth. The bar I! is normally positioned along the side wall, as shown in Figures 1 and 2, being retained by a detent clasp 26.

A convenient observing depth is cm., al-' though other depths, preferably between 2 and 10 -cm., may be employed. As a result of using an observing depth of several centimeters it is possible to add a smaller quantity of the indicator than is practical in -the usual methods of colorimetry, in which the unknown is observed through a lesser depth. The use of very low concentrations of indicator is advantageous because it reduces the errors caused by the fact that the pH of the indicator is usually not the same as that of the unknown. When working with unbuifered unknowns, such as water, errors due to this cause may often be too great to be neglected,

unless extremely low concentrations of'the indicator are used.

To adjust the positions of the cups when assembling the instrument, as when one or both of the cups are being replaced, or the cup 12 has been removed from its clamp 13, the cup 6 is placed around the cup l2 .and slid upwardlyabove the level of the bar l3, which is then swung beneath the cup, assuming a position perpendicular to the side wall. are then lowered, the former resting on the spacing bar, and the bottom of the latter resting on the floor of the cup 9. The clamp i 3 is then tightened, the spacing bar is returned to its position adjacent the wall of the cabinet, and the cup 12 is slid downwardly to rest on the floor 5.

The cups are then in the correct relative positions.

To fill the cup 3 or to change the solution therein, the cup is pulled outwardly out of engagement with the clamp, I6, whereby both cups swing about the pin l1, until-the cup 3 is clear of the floor of the cabinet, from which position it may be lowered and withdrawn from the instrument. It is filled to a level slightly higher than the observing depth, which level may be indicated in the case of a glass cup by a mark 2|, raised about the cup l2, pushed back into engagement with the clamp l6 and the edge of the positioning plate H, and slid downwardly to insure its proper seating on the floor. The adjustment of the cup I2 is not disturbed thereby. It will be noted that this arrangement permits the rapid removal of the cup 6 for changing from successive unknowns without necessitating the removal or readjustment of the position ofv the cup I A cup 22, adapted to contain one of the standard solutions which, in the embodiment shown,is the solution containing the indicator transformed to the alkaline form, having a flat, translucent floor,

mounted in fixed relation cup 22 by means of a clamp 26, provided with a The cups 6 and I2 with the floor of the cup 25.

is removably secured to the cabinet by means of a resilient clamp 23 and a positioning plate 24, resting on the floor 5, A telescoping cup 25 having a flat translucent bottom, the other standard solution which, in the embodiment shown, is the solution containing the indicator transformed to the acid form, is eccentrically and telescopically mounted within the cup 22 by means 'of a clamp 26, described below. A third telescoping cup 21, also having a flat transand adapted to contain lucent bottom, so as to function as a translucent plunger dipping into the solution in the cup 26 is to the bottom of the flat facet 23 adjacent the face i4 of the clamp l3. The clamp 28 is removably attached to'the adjacent cabinet wall by means of a T-shaped lug 36, slidably supported by a slotted track 3| attached to the wall, whereby the vertical position of the clamp 26 with respect to the floor 5 is fixed.

A dial 32 on the front of the cabinet is mounted on a shaft 33, Journaled in the front wall of the cabinet. The shaft carries a spur gear 34, engaging a rack 35, secured to the wall by means of cleats 36. The rack 35 carries a block 31, provided with holes 33, shaped to frictionally engage resilient prongs 33 on the clamp 26. The rack and gear are so constructed as to move the block 31 through a vertical distance equal to the observing depth when the dial sired, predetermined-arc, marked thereon, This are may correspond to one revolution, or may be either greater or less than 360; in the embodiment shown, it is 330, and the limits thereof are indicated by the marks a and b.

To assemble and adjust the cups, the cup 25 is loosely attached to the clamp 26 and placed within the cup 22. The cup 21 is similarly loosely attached to the clamp 26 and placed in the cup 25. The assembly is slid into the cabinet. While sliding it into position, the clamp 26 is engaged with the track 3|; the clamp 26 is then guided by hand to engage the prongs 39 with the block 31, whereby the clamp 26 is supported by the gear and rack- 34, 35. The dial 32 is rotated until the mark a is opposite the reading index c on the front wall 4 of the cabinet, and the cup 25 is lowered until it rests on the floor of the cup 22. The clamp 26 is then tightened. The dial is next rotated until the graduation mark b is opposite the reading index 0, and the clamp 28 is tightened while'the bottom of the'cup 21 is in engagement 25, the clamp 26 is disengaged from the block 31, and the three cups slid outwardly. The cups 22 and 25 are filled to levels slightly in excess of the observation depths; and the three cups are reassembled and slid into the cabinet as described above. The vertical adjustments of the clamps 26 and 26 and of the cups 22, 25, 21 will not be disturbed thereby. The

To fill the cups 22 and cups 22 and 25 may be provided with graduation marks 46 and 4| to aid in filling to the proper levels. When all cups are properly filled, the door 2 is closed to exclude light.

The optical system comprises: the reflector 1; a pair of apertures 42 and 43 of equal sizes in the floor 5 located below'the cups l2 and 21 and of the same diameter as these cups or slightly larger; an elongated hole 44 in the ceiling 3 of the cabinet, extending over the cups l2 and 21; a pair of prisms 45; and an eye piece 46. The eye piece is frictionally secured to 'a support 41 which houses and supports the prisms 45, the support being attached to the cabinet by a pair of resilient prongs 32 is rotated through a de- 4 "a extending downwardly from protrusions 41b on the front and rear of the support (see Figure 3). The prisms are located to translate the rays of light passing upwardly through the cups. so that the light from the cup l2 occupies one half of the field of vision, and the light from the cup 21 the other half. Suitable lenses are mounted in the eye piece.

It should be noted that the eccentric locations of the cups in the cabinet permit the cups I 2 and 21 to be mounted relatively close together, thereby simplifying the optical system, and permitting smaller prisms to be employed. 7

A pair of channel bars 42 below the fioor 5 are adapted to receive a slide containing a colored glass. The use of such a color filter is advantageous with some indicators.

The graduations on the dial 22 are symmetrical about the zero mark (I. which is midway between the marks a and b, and which is opposite the mark 0 when the cup 25 is in its midway position.

The dial is graduated according'to the equation:

wherein a: is the distance between the bottom of the cup 21 and the upper face of the bottom of the cup 25 at any position of the dial, divided by the observing depth: andR is the corresponding reading or graduation on the dial for the point opposite the reading mark or index 0.

It will be evident that the ratio of (1.1:) to :c in Equation 6 is equal to the ratio of the depth of the solution in the cup 22, containing the indicator in the alkaline form, to the depth of the solution in the cup 25, containing the indicator in the acid form, through which the light from the aperture 43 must pass, The value R, therefore, is equal to the first member of the second term of the Equation 4.

If, therefore, the concentration of the indicator in the unknown in the cup 0, and in the solutions in the cups 22 and 25 is the same, the pH of the unknown may be determined by the equation:

wherein R is the reading on the dial when the colors on both sides of the field of vision in the eye piece are the same.

To determine the pH of an unknown, a suitable indicator the constant K: or DKI of which is known, is selected, and small quantities thereof are added to the unknown in the cup 8, and to liquid in the cups 22 and 25.- II the unknown is water, water may be employed in the cups 22 and 25. The amount of indicator is selected so as to cause its concentration in all three cups'to be the same. The liquid in the cup 25 is acidified to transform the indicator to the acid form, as by the addition of a few drops of. a strong mineral acid like H01, and the liquid in the cup 22 is made alkaline by adding a mineral base like-NaOH. The cups are placed into the instrument, the reflector I adjusted to throw a beam of light through the holes 42 and I2, and the dial is rotated until the colors on both sides of the field of vision in the eye piece are matched. The reading on the dial is then added algebraically to the pK: for the indicator.

For example, in the device illustrated, the reading is --0.22. If the indicator has a constant K1=6.8 10.9, or pKr=8.17, the pH of the un-- known is determined by adding 0.22 to 8.17, the answer being 7.95. For successive unknowns of approximately the same pH, the standard solu-.

tlons may be re-used, it being only necessary to I change the liquid in the cup I.

rp ing a 21 easily without disturbing the adjustment or the 1 cup with respect to its clamp and to the cup 22. The dial may be constructed so as to perform the addition of the reading and the rectly. Such a dial is illustrated in Figures 8 and 9. It comprises a circular base 55, having a central hole for receiving the shaft 22, and

mounted by a smaller annular disc 52, held in positign by a shim and a knurled threaded nut 5 A pointer 55 is mounted on the front wall 4 of the cabinet by means of the bolts 51 passing through an elongated slot in the pointer, whereby the pointer can slide vertically.

The annulararea of the base surrounding the disc 52 carries eleven concentric circles. The first and eleventh (inner and outer) circles are similarly subdivided by points corresponding to even tenths of the value of R according to Equation 6., Thus, the dial illustrated in Figure 8 was constructed by solving the Equation 6 to obtain a series of values of :1: which correspond to the following values of R: -1.20, 1.10, 1.00, -0.90, etc., up to +120. Points corresponding to values of R from 1.10 to +1.20 were marked on the inner circle similarly to Figure 7, i. e., the dial was rotated to cause the movable cup 22 to have the position for which a: is equal to the particular value of z being plotted, and a graduation was made on the dial on the inner circle opposite the pointer 55. The magnitudes of the values of R were not, however, indicated .on the base 50. It will be noted that when R=0.00, x=0.500; this point is at the middle 01' the scale, opposite the index mark (1. The outer circle was similarly graduated, with the diflerence that points corresponding to values of R from l.20 to +1.10 were plotted. The intermediate circles are also callbrated by the Equation 6, but the points thereon correspond to intermediate values of R, as follows: On the second circle (adjacent the inner circle) the points correspond to values of R equal to an even tenth plus 0.09 (or 0.01); on the third circle, to values of R equal to even tenths plus 0.08 (or 0.02), etc., so that the points on the tenth circle (adjacent the outer circle) correspond to values of R equal to even tenths plus 0.01 (or --0.09). Thus, in graduating the second circle of the dial illustrated, the Equation 6 was solved to obtain a series of values for a: for which R had the values: 1.11, -1.01, 0.91, etc., up to +1.19, and these points were plotted on the second circle in the manner described above. Heavy curves e join points on the concentric circles as shown. For ease in interpolating, additional lighter curves f are placed intermediate some of the curves e. These correspond to values of R differing by 0.05 from those indicated by the solid curves e.

The annular portion of the disc 52 surrounding the disc 52 is uniformly subdivided into thirty number 8 to be in the readings. Lines 9 on the base 55 connect the inner termini of the heavy curves. e

to the equally spaced numbers on the disc 52. By rotating the disc 52 with respect to the base 56 it is possible to indicate the curves e by any.

number from to 9. a

The annular disc 53 carries numbers from 1 to 13, uniformly spaced about the circumference to indicate units in the reading. Thelines h on the disc 52 join the three 0's thereon to three adjacent numbers on the disc 53. By rotating the disc 53 with respect to the disc 52, it is possible to indicate the 0's on the latter by any three consecutive numbers from 1 to 13.

The marks a, b and d are the same'as for the dial 32 shown on Figure '7.

To use the m1, it is adjusted by means or the set screw 5i to cause the mark d to be opposite the pointer 56 when the cup 25 is in its midway position, as in the dial according to Figure 7. With the dial in this position, the discs 52 and 53 and the pointer 56 are adjusted to yield a reading equal to pKr for the indicator employed. For example, when cresol red, having 9. PK! value of 8.17 is employed, the 'disc 52 is moved to cause the number 1 (corresponding to the tenths) to be joined by a line g to the line 6 which intersects the inner circle opposite the mark d; the disc 53 is moved to cause theunit joined by a line it to the 0 on the disc 52 next to the left of the said number 1; and the pointer 56 is moved radially to point to a circle on which the value 8.17 is read to the nearest hundredth. This circle is found to be the eighth circle (seventh from the inner circle). These adjustments are shown on Figure 8, save that the dial is not positioned with the index mark opposite the pointer 56.

Referring to Figure 8, it will be observed that when the dial is turned counter-clockwise to bring the mark d under the center line of the pointer 56, the tip of the pointer will indicate 8.17 as follows 'The heavy curve e which in that position appears to the left of the pointer indicates the first two digits of the number, i. e., 8.1, the digit 8 being read on the innermost disc 53, and the digit 1 being read on the annular disc 52. The last digit 1 is interpolated along the eighth circle between the aforesaid heavy curve e and the adjacent curve e to the right of the pointer. These adjustments for the discs 52 and 53 and for the pointer 56 having been made, they are not changed. so long as the same indicator or an indicator having the same constant is employed.

To determine the pH of an unknown the cups are filled and the dial is rotated as described above in connection with Figure 7 so that the color on each side of the field of vision in the eyepiece is the same. When'this setting of the dial has been obtained the pH may be read thereon directly. For example, when the final position of the dial is as shown in Figure 8, the pH is read as 1.95. This is read at the tip of the pointer on the eighth circle as follows: The first two digits of the pH, i. e., 1.9 are indicated by the heavy curve e to the left of the pointer, these digits being given by the discs 53 and 5" The last digit 5 is interpolated between the aforesaid heavy curve e and the heavy curve e to the right of the pointer, the latter curve having the value 6.0.

Any number of unknowns may be tested with radial position of the pointer 56 must be is equal to the the same indicator and with the same adjustments of'the discs 62, 63 andthe pointer 56. When an indicator having a diflerent constant is employed the angular positions of the discs 52 and 53 with respect to the base 56, and the 5 altered so that the value of'the indicator constant is read at the tip of the pointer when.the dial is positioned to cause the mark if to be in line with the pointer 56 as explained above. It shouldbe noted that the lines a and hand the discs 52 and 63 are merely for the purpose of facilitating the reading of the units and tenths in the value of the pH, and that either or both of these discs may-be omitted without destroying the utility of the curves e and the pointer 56, since it \is possible for the operator to remember the units and the tenths. It should also be noted that the dial according to Figures 8 and 9 may'also be used in the manner described for the dial 32, using only the first or eleventh circle. Moreover. the graduations of the dials 32 and/or 56 need not be inscribed on a circular dial, it being possible to employ any other shape of scale, without depiarting from the spirit and scope of the invent on.

A modification of the colorimeter is illustrated in Figures 10 to 18, differing from the form described above in the manner of mounting the cups, and in the mechanical arrangement for varying and reading the. position of the movable cup. Referring to these figures, the apparatus comprises a cabinet 66, provided with a door 61, a ceiling 62, a partition wall 63, side walls 64 and 65, and a fioor 66. The floor and ceiling are pro- 85 vided with apertures, as described in connection with Figures 1 to 7, and the optical system is the same.

A pair'of cups 61 and 66, similar to the cups 6 and 22, is removably mounted within the cabinet by means of resilient clamps 66 and 16, resting on the floor 66, against positioning plates 1| and 12, adapted to contain the unknown solution and the solution containing the indicator transformed to the alkaline form, respectively. The clamp 10 is attached to the wall 63 through a stirrup 16a (see Figure 11) which spans the slide 64, described below. A pair of smaller telescoping cups 13 and 14, corresponding to the cups i2 and21, respectively, are mounted within the cups 61 and 5 66 and eccentrically thereto, as shown. They difler from the cups heretofore. described in that they are provided with annular flanges or beads 15 and 16 at their upper ends, which may be integral with the cups, or may be in the form of 5 metallic bands fitted thereto. A pair of horizontal supporting bars 11 and 16 are fixed to the partition wall 63, and are provided at their ends with channelled sockets 16 to receive the flanges of the cups, as shown more particularly in Figure 14. Leaf springs 66 may be provided to retain the cups removably in the supporting bars.

, The sizes of the cups and the locations of the bars 11 and 16 are such that the cups are always in the proper relative positions, as described above in connection with Figures 1 to '1. Thus, the vertical distance between the bottom of the cup 13 and the upper surface of the floor of the cup 61 observing depth; and the distance between the bottom of the cup 16 and the upper surface of the floor of the cup 66 is equal to the observing depth plus the thickness of the floor of the movable cup 61, described below.

The movable cup 6| is telescopically mounted between the cups 66 and 16, and is similarly provided with a flange or bead 82, engageable with a supporting bar 88, constructed similarly to the bar 11, shown in Figure 14. The bar 88 is attached to a slide 84, secured to the wall 88 by means of studs 88, and vertically slidable with respect to the wall.

A lever 88 is pivotally supported by the partition wall 88 by means of a shaft 81, provided with a spring 88 arranged to raise the longer arm 88 nearest the movable cup, and of sufficient stiflness to raise the movable cup, together with its slide and supporting bar and to overcome friction. The longer arm 88 has a bifurcated end, engaging a roller 80, surrounding a pin 8I on the slide 84. The shorter arm 82 carries a roller 88, constantly urged to engagement with a cam 84 by the action of the spring 88. The lever 88 is shaped to cause the centers of the pin 8| and the shaft 81 to be in line with the lower edge of the roller 88. Any convenient ratio of lengths of lever arms may be employed, and the arms may be of equal lengths. It is, however, generally desirable to magnify the action of the cam 84, and I prefer to locate the shaft 81 nearer to the cam than to the pin 8i, as shown.

The wall 68 is provided with a bushing 85, which houses a shaft 86 carrying the cam 84 at one end, and a knob 81, at the other end. The knob 81 is provided with a set screw 88, which fits into a groove in the shaft for properly orienting the knob when the latter is loosened or removed for re-orienting or reversing the graduated disc. The knob 81 carries a transparent disc 88 having a reading line is. A graduated disc I is mounted around the bushing between the wall 88 and the disc 88, being secured against rotation by means of a pair of orienting pins IN on the outer surface of the wall 65, and entering holes I02 in the disc I 00. The disc I00 is opaque, and may be graduated on both sides, as described below.

As shown in Figure 15, the obverse of the disc I00 is marked with a plurality of concentric circles m, one circle being provided for each of the most commonly used indicators. Any uniform scale may be used for the calibration of these circles, as discussed below. In the embodiment shown, these circles are calibrated uniformly so that 1.0 unit of pH corresponds to an arc of whereby a spread of two units of pH may be read. The origin of these graduations is a vertical line n, and the graduation at the line n corresponds to the pK: value for the indicator in question at the ionic strength of electrolytes most commonly encountered in the laboratory in which the instrument is to be employed, and for the temperature to be used. The reverse 'of the disc may be similarly graduated for other conditions or indicators, the graduations increasing clockwise.

The cam 84 has a bevelled edge, the bevel angle varying to cause the roller 88 to engage the entire edge at any position of the cam. The outline of the surface of the cam nearest the pivot shaft 81 is such as to have a curve defined by the equation:

C9-l0g (8) wherein 9 is the angular displacement in degrees of arc of the reading line It from the origin line 11 on the disc I00 at any setting of the cam, taken positive when the line It is displaced clockwise, as shown, and negative when displaced counterclockwise; C is a constant dependent upon the range of pH values to be indicated on the disc; L is a constant equal to the leverage (i. e., the ratio of the length of the arm 88 to the length of the arm 88) divided by the observing depth; and P is the radial distance from a reference circle of origin q to the curve defining the cam edge, as shown in Figure 13, the distance P being measured along a radius passing through the point of contact of the roller 88 at the particular setting of the cam and disc 88. In the embodiment shown, in which a complete circle on the disc I88 corresponds to 2.0 units of pH, C=1/180; also,-

the leverage is shown to be 2, so that if the observing depth is 5 cm., the constant L equals 0.4, P being expressed in centimeters.

The slide 84, support 88, lever 88 and cam 84 are so constructed that the cup 8| is in its mid way position when the line kl" on the disc 88 is coincident with the line '12 on the disc I00, PL being in this position equal to 0.50. It follows from this construction that the movable cup 8| will be moved by the rotation of the shaft 88, disc 88 and cam 84, and that the angular displacement of the reading line It from the origin line 11 will be directly proportional to the first member of the second term of the Equation 4. The graduations of pH on the disc I00 may, therefore, be linear, and the pH may be read directly, the cups being filled and the colors matched with the aid of the eye piece as described above.

For example, in the device illustrated, the cup is positioned so that the ratio of the depth of alkaline to the depth of acid form of the indicators in the cups 88 and 8| is 1.072, and the corresponding value of 9 is +528, so that C equals +0.03. If bromcresol green is the indicator, the pH of the unknown is 4.73; if bromthymol blue is the indicator, the pH is 7.16.

To obtain readings for conditions or indicators other than those provided on the concentric circles of the disc I08, an outer ring of spaced reading marks 8 numbered twice to 9 is provided. The disc I00 is provided with twenty orienting holes I 02, uniformly spaced on the circumference of a circle. It is thus possible to orient the disc I08 in any desired position, whereby any even graduation from 0 to9 can be brought to the top of the disc opposite the reference mark t on the wall 85. An arm I08 having a flducial edge u is frictionally and rotatably attached to the knob 81, andv can be moved through an arc corresponding to the distance between adjacent marks s, i. e., about 18. As shown in Figures 11, 12 and 16, the face of the knob 81 which is adjacent to the disc 88 is cut away at 81a so as to provide a recess for receiving the arm I08. The recess 81a is in the shape of a sector, thereby permitting a limited angular movement between the knob 81 and the arm I08 for adjustment. In the normal operation of the instrument the arm I08 is fixed with regard to the knob 81, moving together with it when the knob is rotated.

To use the outer ring of graduations, the knob 81 is loosened and slid away from the wall 88; the disc I00 is oriented to bring the mark s corresponding to the nearest tenth of the pK: value of the indicator opposite the mark t; the knob 81 is then secured in engagement with the disc I88. With the shaft positioned to bring the reading line It directly over the origin line 11, the flducial edge of the arm I08 is set to indicate the pK: to the nearest hundredth. Units and hundredths of rom 0 pH may then be read on the outer ring of gradupH of the unknown or 11.00.

at any position of I00 is adjusted for an indicator having a pKr oi 10.70.

(These settings are also correct for an indicator having a pKr of 0.70). The knob 01 is, in this' figure, positioned to yield a reading for the (I! the pK: oi the inadcator were 0.70, the pH reading would be 1.

I claim as my invention:

1. A colorimeter comprising acabinet providing a dark chamber, a first cup within said cabinet having a fiat translucent bottom and adapted to contain a sample of unknown color, a translucent ceiling tor said cup spaced from the bottom thereof by a predetermined observing depth, a second cup having a fiat translucent bottom located adjacent to said first cup within said cabinet and adapted to contain a first color sample, a third vertically movable cup of smaller cross-sectional area than said second cup and telescopically mounted -therein, having a fiat translucent bottom and adapted to contain a second color sample, a normally stationary translucent plunger of smaller cross-sectional. area than said third cup mounted telescopically therein, said third cup and plunger being mounted eccentrically with respect to the second cup and towards said first cup, means for moving said third cup vertically, whereby the ratio of the depth of the color sample in said second cup beneath said third cup to the depth oi'the color sample in said third cup beneath saidplunger can be varied, a graduated scale means operatively connected to said third cup for indicating on said scale a reading it defined by the equation where a: is the ratio or the depth 01' the color sample in said third cup to the sum of said depths of the color samples, means for transmitting a first beam of light through the sample in the first cup, means for transmitting a second beam of light through said depths of color samples in the second and third cups and through the said plunger, an eyepiece, and prism means retracting said beams of light into said eye piece.

2. The colorimeter according to claim 1 in which the sum of the said depths of the color samples is equal to the'said observing depth.

3. A colorimetercomprising a first cup having a translucent bottom' and adapted to contain a first sample provided with means to interpose apredetermined depth or said sample to a substantially vertical first beam of light, telescoping second and third relatively vertically movable cups of different cross-sectional areas having translucent bottoms, located adjacent to said first cup and adapted to contain second and thirdsamples and provided with means'to interpose a constant predetermined total depth of said second and third samples to a second substantially vertical beam of light, means for effecting relative vertical motion between said second and third cups, and means comprising-a graduatedscale operatively connected to said second and third cups for indicating on said scale a reading R defined by the equation scale-carrying arranged by said 7 where :r is the ratio of the' depth oi! said third sample interposed to. said second beam of light-to said constant predetermined depth.

4. A colorimeter comprising afifst receptacle having a translucent portion adapted to contain a material or unknown color and arranged to interpose a predetermined observing depth 01' said solution to a first beam of light, a pair of second and third recptacles having translucent portions adapted to contain two samples of different colors and arranged to interpose' said samples 'to a second beam or light, means for varying the ratio oi the depths oi. said samples interposed to said second beam of light while maintaining the sum of said depths or samples constant, a graduated scale, and means operatively connected to said receptacles for indicating on said scale a reading It defined by the equation where a: is the ratio of 'the' depth of one 01 said samples to said sum oi the depths.

5. The colorimeter according to claim 4 in which the said sum of the depths of the samples interposed to the second beam of light is equal to the observing depth.

6. In a colorimeter, the combination oi. two receptacles having translucent portions adapted to contain samples of diiierent colors and arranged to inter-pose said samples to 'a beam or light, means iorvarying the ratio of the depths of said samples interposed to said beam or light while maintaining the sum oi! said depths of samples constant, a graduated scale, and means operatively connected to said receptacles for indicating on said scale a reading R defined by the equation R=log where a: is the ratio of the depth oi one of said samples to said sum of the depths. I

7. The combination accordingto claim 6 in which the scale and indicating means comprise a body and a reading index associated therewith, said index and scale-carrying body being movable relatively to one another, and operative connection to said receptacles to cause the relative movement to be linearly proportional to the depth of one oi the said samples interposed to said beam oi. light, said scale being graduated to yield the reading R opposite said index.

8. In a colorimeter, the combination 01 two receptacles having translucent portions adapted to contain samples of different colors and arranged to interpose said samples to a beam of light, means for varying the ratio of the depths of said samples interposed to said beam of light while maintaining the sum 01' said depths constant, a scale carrying body carrying a plurality of scales, and a reading index arranged to permit a reading on any selected scale, said index and scale carrying body being movable relatively to one another and being operatively connected to said receptacles to cause the relative movement 8.101;: the scales to be linearly proportional to the dep beam of light, each 0! said scales being subdivided by graduations corresponding to equicrescent values or R defined by the equation:

R=1og of one of said samples interposed to said determined where a: is the ratio of the depth of one of said samples to said sum of the depths, and successive scales being graduated values of R. I

9. The colorimeter according to claim 6 in which the scale bears equally spaced divisions 'of R and the means for indicating the reading R thereon comprises a cam operatively connected to said receptacles, a shaft for said cam, the cam surface being shaped to cause the angular displacement of the shaft to be proportional to R.

10. A colorimeter comprising a first receptacle provided with spaced translucent surfaces adapted to interpose a predetermined depth of a first sample to a firstbeam of light, three telescoping cups provided with translucent bottoms the lower two of which form second and third receptacles for second and third color samples, the uppermost and lowermost mally relatively fixed and the intermediate cup being vertically movable, whereby a constant pretotal depth of said second and third samples may be interposed to a second beam of light passing through the bottoms of said telescoping cups, a vertically movable support for said intermediate cup, a rotatable shaft mechani-.

cally connected to said support to cheat a simultaneous motion of the support and of the shaft, and a scale and reading index operatively connected to said shaft graduated to yield a'reading R on the scale defined by the equation R=log where a: is the ratio of the depth of said third sample interposed to said second beam of light to said constant predetermined total depth.

11. The calorimeter according to claim 10 in which the shaft is connected to the movable support so as to cause its angular position and the displacement of the index with respect to the scale to be linearly proportional to the vertical position of said intermediate cup.

12. The colorimeter according to claim 10 in which the scale bears equally spaced graduations, said scale and index being operatively connected to said support to cause the displacement of the index with respect to the scale to be proportional to the logarithm of said ratio.

13. A colorimeter comprising a first receptacle provided with spaced translucent surfaces adapted to interpose a predetermined depth of a first sample to a first beam of light, a pair of telescoping cups provided with translucent bottoms, forming second and third receptacles for second and third color samples, a translucent plunger depending into the upper cup and normally fixed relatively to the lower cup and the upper cup being vertically movable relative to the lower cup, whereby a constant predetermined total depth of said second and third samples may be interposed to a second. beam of light passing through the bottoms of said telescoping cups, a vertically movable support for said upper cup, a cam mounted on a rotatable shaft, a lever in engagement with a surface of said cam and with said movable support, arranged to position the latter in accordance with the position of said cam, said cam surface being shaped to cause the angular displacement of said shaft to be proportional to the logarithm of the ratio of the depths of said second and third samples interposed to said second beam of'light, a scale graduated in equally spaced divisions of R and index means operativetodiflerent series of of said cups being norr tosaidshaftfor sai e,defined ly connected to said scale and where a: is the ratio of the depth of said third sample interposed to the second beam of light to said constant predetermined total depth.

14. A colorimeter comprising a first receptacle provided with spaced translucent surfaces adapted to interpose a predetermined depth of a first sample'to a first beam of light, a pair of telescoping cups provided with translucent. bottoms, forming second and third receptacles for second and third color samples, a translucent plunger depending into the upper cup and normally fixed relatively to the lower cup and the upper cup being vertically movable relative to the lower cup, whereby a constant predetermined total depth of said second and be interposed to a second beam of light passing through the bottoms of said telescoping cups, a vertically movable support for said upper cup, a rotatable shaft mechanically connected to said support to effect simultaneous motions of the support and of the shaft such that the angular displacement of the shaft i'sproportional to the logarithm of the ratio of the depths of said second and third samples interposed to said second beam of light, a normally stationary disc surrounding the axis of said shaft, means for securing said disc in any one of a plurality of angularly spaced positions, a scale on said disc graduated in-equally spaced divisions of R and a reading in- R=log where a: is the ratio of the depth of said third third samples may sample interposed to the second beam of light to said constant predetermined total depth.

15. The colorimeter according to claim 14 in which the reading index is angularly adjustable with respect to the shaft to increase or decrease the readings on the scale by a predetermined quantity. i

16. In a colorimeter, the combination of two receptacles having translucent portions adapted to contain samples of different colors 'and arranged to interpose said samples to a beam of 'light, means for varying the ratio of the depths of said samples interposed to said beam of light while maintaining the sum of said depths equal to a distance A, a dial operatively connected to said receptacles to have an angular displacement which is proportionalto B, the depth of one of said samples, a scale on said dial calibrated in successive values of R by the equation:

R=log i 1PL PL where C and L are constants, 9 is the angle between a radial line of origin and a radius from the cam axis to the surface, and P is the distance between a reference circle concentric with the shaft and said cam surface measured along said radius, a pair of receptacles having translucent portions adapted to contain samples of difierent colors and arranged to interpose varying depths of said samples to a beam of light, and means operatively in engagement with said cam surface for varying one of said depths in accordance with said cam surface as the shaft is rotated.

WIIFRED F. LANGELIER.

Certificate of Correction Patent No. 2,216,976. October 8, 1940. WILFRED F. LAN GELIER It is hereby certified that errors appear in the printed specification of the above numbered atent requiring correction as follows: Page 2, first column, line 44, in the equation, or before log read page 4, first column, line 72, for K 6.8X10.9 read K =6.8 10 and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 3rd day of December, A. D. 1940.

HENRY VAN ARSDALE,

Acting Commissioner of Patents. 

